Solidothermal synthesis of a boron-containing zeolite with an mww framework structure

ABSTRACT

The present invention relates to a process for the production of a zeolitic material having an MWW framework structure comprising YO 2  and B 2 O 3 , wherein Y stands for a tetravalent element, said process comprising
         (i) preparing a mixture comprising one or more sources for YO 2 , one or more sources for B 2 O 3 , one or more organotemplates, and seed crystals,   (ii) crystallizing the mixture obtained in (i) for obtaining a layered precursor of the MWW framework structure,   (iii) calcining the layered precursor obtained in (ii) for obtaining the zeolitic material having an MWW framework structure,   wherein the one or more organotemplates have the formula (I)       

       R 1 R 2 R 3 N   (I)
         wherein R 1  is (C 5 -C 8 )cycloalkyl, and   wherein R 2  and R 3  are independently from each other H or alkyl, and   wherein the mixture prepared in (i) and crystallized in (ii) contains  35  wt.-% or less of H 2 O based on 100 wt.-% of YO 2  contained in the mixture prepared in (i) and crystallized in (ii), as well as to a synthetic boron-containing zeolite which is obtainable and/or obtained according to the inventive process and to its use.

TECHNICAL FIELD

The present invention relates to a process for the preparation of azeolitic material having an MWW framework structure comprising YO₂ andB₂O₃, wherein Y stands for a tetravalent element, wherein said processinvolves the solidothermal crystallization of a mixture containing 35wt.-% or less of H₂O based on 100 wt.-% of YO₂ contained therein.Furthermore, the present invention relates to a zeolitic material havingan MWW framework structure obtained and/or obtainable according to saidprocess, as well as to its use in particular applications.

INTRODUCTION

Zeolites are microporous crystalline solids which are characterized by awell-defined pore or cavity or channel structure of moleculardimensions. Zeolites have been widely used in petro-chemistry (e.g.,fluid catalytic cracking and hydrocracking), ion exchange (e.g., watersoftening and purification), and in the separation and removal of gasesand solvents. The industrial application value of a zeolite is generallyassociated with its structure uniqueness as well as the production costof the zeolite. Notably, some zeolitic materials, for example, with anMFI, FAU, or MOR framework structure, have been found to be veryversatile in industrial applications, since the chemical properties ofsuch zeolites can be tuned for meeting different requirements.

Among the zeolitic frameworks discovered in recent years, the MWWstructure has attracted considerable attention in both academic researchand practical applications. The MWW frame-work structure ischaracterized by two independent pore systems. Specifically, one poresystem comprises two-dimensional sinusoidal 10-member ring (10-MR)channels with an elliptical ring cross section of 4.1 A×5.1 A. The otherpore system comprises large 12-MR super-cages connected by 10-MRwindows. More structural details of the MWW framework structure weredescribed by M. E. Leonowicz et al. in Science, vol. 264 (1994), pages1910-1913. Besides said unique structural features, it is also notedthat MWW zeolites are synthesized by first forming layered precursorsintercalated with organic template molecules after a crystallizationprocess. Upon a further calcination, the dehydroxylation andcondensation between the two dimensional layered precursors lead to theformation of the zeolitic product with a three-dimensional MWWframework.

Owing to the unique combination of 10-MR and 12-MR channel systems, MWWzeolites, in particular aluminosilicate MCM-22, have been investigatedas shape selective catalysts for hydro-carbon conversions, also asadsorbents for separation and purification processes in the petroleum,petrochemical and refining industries. For example, U.S. Pat. No.5,107,047 discloses the application of zeolite MCM-22 for isomerizationof olefins. Similarly, U.S. Pat. No. 4,992,615 discloses alkylation ofiso- and ethyl benzene in liquid phase by alkylation of benzene withpropylene.

The synthesis of zeolite MCM-22 has already been extensivelyinvestigated. For example, U.S. Pat. No. 4,954,325 A discloses thesynthesis of zeolite MCM-22 using hexamethyleneimine as anor—ganotemplate under hydrothermal conditions at a temperature in therange of 80-225° C. for 24 hours to 60 days. However, the disadvantageof using hexamethyleneimine as an organotem-plate is thathexamethyleneimine is highly toxic and expensive, which render itunsuitable for a large scale synthesis of MWW zeolites including MCM-22.

U.S. Pat. No. 5,173,281 A relates to the synthesis synthetic porouscrystalline materials employing organic structure directing agents,wherein in particular aminocyclohexane, aminocyclopentane,aminocycloheptane, 1,4-diazacycloheptane, and azacyclooctane areemployed. U.S. Pat. No. 5,284,643 A concerns the preparation ofGa-containing MCM-22, wherein although hexamethyleneimine isspecifically employed as a structure directing agent, aminocyclohexane,aminocyclopentane, aminocycloheptane, 1,4-diazacycloheptane, andazacyclooctane, amongst others, are also mentioned as possible organicstructure directing agents.

WO 2015/185633 A, on the other hand, teaches a facile and inexpensivemethod for the production of a material with an MWW framework structurewhich employs specific cycloalkylamine organotemplates with the seedcrystals.

Although several processes exist for synthesizing boron-containingzeolites with an MWW framework structure, there still remains a need forfurther improving the synthetic processes to obtain such zeolites.Recently, Ren et al. in J. Am. Chem. Soc. 2012, 134, 15173-15176 and Jinet al. in Angew. Chem. Int. Ed. 2013, 52, 9172-9175 reported thesolvent-free synthesis of aluminosilicate and aluminophosphate-basedzeolites, emphasizing the advantages linked thereto such as increasingzeolite yield, reducing water pollution, and eliminating high pressureconditions encountered in conventional synthetic methodologies. Theimportance of solvent-free synthetic methodologies has also beenhighlighted by Morris et al. in Angew. Chem. Int. Ed. 2013, 52,2163-2165.

Wu et al. in J. Am. Chem. Soc. 2014, 136, 4019-4025 relates to thesolvent-free synthesis of zeolites in the absence of organotemplates,and in particular of ZSM-5 and beta zeolite. WO 2014/086300 A concernsthe organotemplate-free solid-state synthetic method for zeolitemolecular sieves and in particular to ZSM-5, beta zeolite, and tozeolitic materials having the FAU, MOR, GIS, and LTA frameworkstructures. WO 2016/058541 A relates to the solidothermal synthesis ofzeolitic materials, and in particular to those having the MFI, BEA, EUO,TON, MTN, ITH, BEC, and ITW framework structures.

Compared with the conventional synthesis, the solidothermal synthesisnot only has all advantages associated with solvent-free synthesis, butalso uses minimal organic templates. Said synthetic methodologies arehowever limited to the direct synthesis of particular types of zeoliticmaterials displaying specific framework structure types.

DETAILED DESCRIPTION

It was therefore the object of the present invention to provide animproved process for the preparation of zeolitic materials having an MWWframework structure comprising YO₂ and B₂O₃, wherein Y stands for atetravalent element, and in particular for Si. Thus is has quiteunexpectedly been found that the layered precursors of the MWW frameworkstructure may be prepared according to a solidothermal process whichdoes not employ a solvent. This was particularly surprising given thefact that said layered precursors do not display the three-dimensionalcvalently bound structure of zeolitic materials, but may only betransformed therein by employing an additional calcination step leadingto the condensation of the hydroxyl groups on the surfaces of adjacentlayers to the final MWW framework structure. Thus, it has quiteunexpectedly been found that a solidothermal methodology may be employedfor the preparation of zeolitic precursor materials and in particular tothe production of a layered zeolitic precursor of the MWW frameworkstructure which does not display the long range 3-dimensional frameworkstructure of a covalently bound zeolitic framework, but rather consistsof arrays of loosely associated 2-dimensional layers which are highlyhydrophilic due to the high content of hydroxyl moieties located on thesurfaces facing the respective layers. In particular, it was completelyunexpected to find that the synthesis of such hydrophilic structurescontaining high amounts of hydroxyl groups may be formed undersolvent-free conditions.

Therefore, the present invention relates to a process for the productionof a zeolitic material having an MWW framework structure comprising YO₂and B₂O₃, wherein Y stands for a tetravalent element, said processcomprising

(i) preparing a mixture comprising one or more sources for YO₂, one ormore sources for B₂O₃, one or more organotemplates, and seed crystals,

(ii) crystallizing the mixture obtained in (i) for obtaining a layeredprecursor of the MWW framework structure,

(iii) calcining the layered precursor obtained in (ii) for obtaining thezeolitic material having an MWW framework structure,

wherein the one or more organotemplates have the formula (I)

R¹R²R³N   (I)

wherein R¹ is (C₅-C₈)cycloalkyl, and

wherein R² and R³ are independently from each other H or alkyl, and

wherein the mixture prepared in (i) and crystallized in (ii) contains 35wt.-% or less of H₂O based on 100 wt.-% of YO₂ contained in the mixtureprepared in (i) and crystallized in (ii).

According to the present invention, the mixture prepared in (i) andcrystallized in step (ii) contains 35 wt.-% or less of H₂O based on 100wt.-% YO₂. Thus, there is no particular restriction relative to theamount of H₂O contained in the mixture prepared in (i) and crystallizedin step (ii) provided that it does not exceed the amount of 35 wt.-% orless of H₂O based on 100 wt.-% of YO₂. Thus, by way of example, themixture prepared in (i) and crystallized in step (ii) may contain 30wt.-% or less of H₂O based on 100 wt.-% of YO₂ contained in the mixtureprepared in (i) and crystallized in step (ii), wherein preferably themixture contains 25 wt.-% or less of H₂O, more preferably 20wt.-% orless, more preferably 25 wt.-% or less, more preferably 10 wt.-% orless, more preferably 5 wt.-% or less, more preferably 3 wt.-% or less,more preferably 1 wt.-% or less, more preferably 0.5 wt.-% or less, morepreferably 0.1 wt.-% or less, and more preferably 0.05 wt.-% or less.According to the inventive process it is however particularly preferredthat the mixture prepared in (i) and crystallized in step (ii) contains0.01 wt.-% or less of H₂O based on 100 wt.-% of YO₂ contained in themixture prepared in (i) and crystallized in step (ii).

Although there is principally no limitation as to the components whichmay be provided to the mixture in step (i) in addition to the one ormore sources of YO₂, one or more sources for B₂O₃, one or moreorganotemplates, and seed crystals, it is preferred that the mixtureprepared in (i) and crystallized in step (ii) does not contain more thana particular amount of specific elements. Thus, by way of example, it ispreferred that the mixture prepared in (i) and crystalized in step (ii)contains not more than a specific amount of fluoride. More specifically,it is preferred according to the inventive process that the mixtureprepared in (i) contains 5 wt.-% or less of fluoride calculated as theelement and based on 100 wt.-% of YO₂ contained in the mixture preparedin (i) and crystallized in step (ii), wherein more preferably themixture prepared in (i) contains 3 wt.-% or less, more preferably 2wt.-% or less, more preferably 1 wt.-% or less, more preferably 0.5wt.-% or less, more preferably 0.1 wt.-% or less, more preferably 0.05wt.-% or less, more preferably 0.01 wt.-% or less, and more preferably0.005 wt.-% or less of fluoride calculated as the element and based on100 wt.-% of YO₂ contained in the mixture prepared in (i) andcrystallized in step (ii). According to the inventive process it ishowever particularly preferred that the mixture prepared in (i) andcrystallized in step (ii) contains 0.001 wt.-% or less of fluoride basedon 100 wt.-% of YO₂ contained in the mixture prepared in (i) andcrystallized in step (ii). Within the meaning of the present invention,“fluoride calculated as the element” refers to the single element, i.e.to the monoatomic species F as opposed to F₂.

According to the present invention it is yet further preferred that themixture prepared in (i) and crystallized in step (ii) does not containmore than a specific amount of phosphorous and/or Al. In particular, itis further preferred that the mixture prepared in (i) and crystallizedin step (ii) contains 5 wt.-% or less of P and/or Al calculated as therespective element and based on 100 wt.-% of YO₂ contained in themixture prepared in (i) and crystallized in step (ii), wherein morepreferably said mixture contains 3 wt.-% or less of P and/or Al, andmore preferably 2 wt.-% or less, more preferably 1 wt.-% or less, morepreferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or less, morepreferably 0.05 wt.-% or less, more preferably 0.01 wt.-% or less, andmore preferably 0.005 wt.-% or less. According to the inventive processit is particularly preferred that the mixture prepared in (i) andcrystallized in step (ii) contains 0.001 wt.-% or less of P and/or Alcalculated as the respective element and based on 100 wt.-% of YO₂contained in the mixture prepared in (i) and crystallized in step (ii).

Within the meaning of the present invention, the term “layeredprecursor” with respect to the zeolitic material having an MWW frameworkstructure refers to a material obtainable and/or obtained in the courseof the synthesis of a zeolitic material having an MWW frameworkstructure with the use of an organotemplate, wherein said precursormaterial is initially crystallized and forms layered precursorsintercalated with the organic template molecules. It is noted that inliterature, layered precursors of zeolitic materials and in particularof zeolitic materials having an MWW framework structure are designatedby the term “(P)” placed after the name of the zeoliteic material havingan MWW framework structure to which it is a layered precursor. Thus, byway of example, the layered precursor to the MCM-22 zeolitic materialhaving an MWW framework structure is designated as MCM-22(P) (cf. e.g.Frontera et al. in Microporous and Mesoporous Materials 2007, Vol. 106,pp. 107-114). From said layered precursor, the zeolitic material havingan MWW framework structure may be obtained by dehydroxylation andcondensation between the two-dimensional layered precursors leading tothe formation of the three-dimensional MWW-framework. Typically, thedehydroxylation and condensation is achieved by thermal treatment of thelayered precursor, in particular by calcination thereof, wherein saidcalcination may be conducted at a temperature in the range of anywherefrom 300 to 900° C., more preferably from 400 to 700° C., morepreferably from 450 to 650° C., and more preferably from 500 to 600° C.As regards the layered precursor obtained in (ii) according to theinventive process, no particular restrictions apply such that inprinciple any conceivable layered precursor may be obtained providedthat it may form a zeolitic material having an MWW framework structureupon calcination thereof in (iii). It is, however, preferred accordingto the present invention that the layered precursor obtained in (ii) isselected from the group consisting of B-MCM-22(P), B-ERB-1(P),B-ITQ-1(P), B-PSH-3(P), B-SSZ-25(P), and mixtures of two ormore thereof,and more preferably from the group consisting of B-MCM-22(P),B-ITQ-1(P), B-SSZ-25(P), and mixtures of two or more thereof. Accordingto the present invention it is however particularly preferred that thelayered precursor comprises B-MCM-22(P) and/or B-SSZ-25(P), andpreferably comprises B-MCM-22(P), wherein more preferably the layeredprecursor obtained in (ii) is B-MCM-22(P).

Concerning the zeolitic material having an MWW framework structureobtained in (iii), on the other hand, again no particular restrictionsapply in its respect such that in principle any zeolitic material havingan MWW framework structure may be obtained in (iii) according to theinventive process, provided that it may be obtained from a layeredprecursor obtained from crystallization in (ii) upon calcination of saidlayered precursor in (iii). It is, however, preferred according to thepresent invention that the zeolitic material having an MWW frameworkstructure obtained in (iii) is selected from the group consisting ofB-MCM-22, B-ERB-1, B-ITQ-1, B-PSH-3, B-SSZ-25, and mixtures of two ormore thereof, and more preferably from the group consisting of B-MCM-22,B-ITQ-1, B-SSZ-25, and mixtures of two or more thereof. According to thepresent invention it is however particularly preferred that the zeoliticmaterial having an MWW framework structure comprises B-MCM-22 and/orB-SSZ-25, and preferably comprises B-MCM-22, wherein more preferably thezeolitic material having an MWW framework structure obtained in (iii) isB-MCM-22.

According to the present invention, the MWW framework structure of theboron-containing zeolitic material comprises Y and oxygen, preferably ina form that the Y atoms are interconnected via oxygen. More preferably,the Y atoms are tetrahedrally coordinated and interconnected via oxygenin the MWW framework structure.

Concerning the Y element in the zeolitic material, no restrictionapplies according to the present invention as to the type or types of Yelement which may be employed, provided that at least a portion thereofmay be incorporated into the MWW framework structure as YO₂. Thus, anyconceivable tetravalent element Y may be employed, wherein said elementis preferably selected from the group consisting of Si, Sn, Ti, Zr, Geand combinations of two or more thereof. Y is however more preferably Siand/or Ti, and is more preferably Si.

According to the present invention, boron is contained in the zeoliticmaterial having an MWW framework, wherein boron is contained in the MWWframework structure of the zeolitic material. Preferably the boron atomscontained in the MWW framework structure are interconnected via oxygen,wherein more preferably, the boron atoms are tetrahedrally coordinatedand interconnected via oxygen in the MWW framework structure.

Step (i)

According to (i) of the present inventive process, one or more sourcesfor YO₂ are comprised in the mixture prepared in said step, Y beingpreferably selected from the group consisting of Si, Sn, Ti, Zr, Ge andcombinations of two or more thereof, wherein Y is more preferably Siand/or Ti, and more preferably Si.

For the preferred embodiments wherein Y is Si in step (i), the one ormore sources for YO₂ in the mixture are one or more sources for SiO₂.

Concerning the one or more sources for YO₂ in the mixture of step (i),again no particular restriction applies in their respect provided thatat least a portion of the YO₂ contained therein or which may be providedby said source by appropriate chemical transformation thereof may beincorporated into the MWW framework structure as SiO₂. According to thepresent invention, said one or more sources of YO₂ are preferablyselected from the group consisting of silicas, silicates, silicic acidand combinations of two or more thereof, more preferably selected fromthe group consisting of silicas, alkali metal silicates, silicic acid,and combinations of two or more thereof, more preferably selected fromthe group consisting of fumed silica, colloidal silica, reactiveamorphous solid silica, silica gel, pyrogenic silica, lithium silicates,sodium silicates, potassium silicates, silicic acid, and combinations oftwo or more thereof, more preferably selected from the group consistingof fumed silica, silica gel, pyrogenic silica, sodium silicates, silicicacid, and combinations of two or more thereof, more preferably selectedfrom the group consisting of fumed silica, silica gel, pyrogenic silica,and combinations of two or more thereof, wherein more preferably the oneor more sources for YO₂ is silica gel.

More preferably, silica gel of the formula SiO₂.x H₂O is employed as thesource for YO₂ in the mixture of step (i). As regards the value of x inthe formula of the silica gel which is particularly preferably used inthe inventive process, no particular restrictions apply provided thatthe mixture prepared in (i) and crystallized in (ii) contains 35 wt.-%or less of H₂O based on 100 wt.-% of YO₂ contained in the mixtureprepared in (i) and crystallized in (ii). Thus, by way of example, x inthe formula SiO₂.x H₂O may be in the range of anywhere from 0.1 to1.165, wherein preferably x is in the range of from 0.3 to 1.155, morepreferably from 0.5 to 1.15, and more preferably from 0.8 to 1.13.According to the present invention it is however particularly preferredthat x in the formula SiO₂.x H₂O is in the range of from 1 to 1.1.

According to step (i) of the present inventive process, one or moreorganotemplates are comprised in the mixture of said step, wherein theone or more organotemplates have the formula (I)

R¹ R²R³N   (I)

wherein R¹ is (C₅-C₈)cycloalkyl, and

wherein R² and R³ are independently from each other H or alkyl.

Concerning group R¹ in formula (I) of the one or more organotemplates,said group is preferably selected from the group consisting ofsubstituted and/or unsubstituted cyclopentyl, cyclohexyl, cycloheptyl,and cyclooctyl, more preferably from the group consisting of substitutedand/or unsubstituted cyclopentyl, cyclohexyl and cycloheptyl, whereinmore preferably R¹ is substituted or unsubstituted cyclohexyl orcycloheptyl, more preferably substituted or unsubstituted cyclohexyl.More preferably, group R¹ in formula (I) of the one or moreorganotemplates is unsubstituted cyclohexyl.

Concerning groups R² and R³ in formula (I) of the one or moreorganotemplates, said two groups are preferably, independently from eachother, H or (C₁-C₃) alkyl. More preferably, R² and R³ are independentlyfrom each other selected from the group consisting of H, methyl, ethyland propyl. More preferably, R² and R³ in formula (I) of the one or moreorganotemplates are H.

According to the present inventive process, it is preferred that the oneor more organotemplates in the mixture of step (i) are selected from thegroup consisting of substituted and/or unsubstituted(C₅-C₈)cycloalkylamines, preferably selected from the group consistingof substituted and/or unsubstituted cyclopentylamine, cyclohexylamine,cycloheptylamine, cyclooctylamine, and combinations of two or morethereof, more preferably substituted and/or unsubstitutedcyclohexylamine and/or cycloheptylamine. More preferably, unsubstitutedcyclohexylamine is the organotemplate in the mixture of step (i).

According to step (i) of the present inventive process, seed crystalsare comprised in the mixture of the said step. Concerning the type ortypes of seed crystals which may be employed in the inventive process,no particular restrictions apply such that any suitable material may beemployed to this effect, provided that it may induce nucleation of thelayered precursor of the boron-containing zeolitic material obtained instep (ii), from which the zeolitic material having an MWW frameworkstructure may then be obtained in step (iii) after calcination thereof.It is, however, preferred according to the present invention that theseed crystals comprise one or more zeolitic materials, whereinindependently from one another said one or more zeolitic materialspreferably comprise YO₂ and X₂O₃ in their framework structure, wherein Xis a trivalent element, and Y is a tetravalent element.

As regards the trivalent element X which may be contained as X₂O₃ in theone or more zeolitic materials preferably comprised in the seedcrystals, no particular restrictions apply such that in principle anysuitable trivalent element X may be employed, provided that it iscontained as X₂O₃ in the zeolitic material's framework structure. It is,however, preferred according to the present invention, that the Xelement in the seed crystals is selected from the group consisting ofAl, B, In, Ga, and combinations of two or more thereof, wherein morepreferably the trivalent element comprises Al and/or B. More preferably,the trivalent element X in the seed crystals is Al.

On the other hand and independently thereof, as regards the tetravalentelement Y which may be contained as YO₂ in the one or more zeoliticmaterials preferably comprised in the seed crystats, no particularrestrictions apply such that in principle any suitable tetravalentelement Y may be employed, provided that it is contained as YO₂ in thezeolitic material's framework structure. It is, however, preferredaccording to the present invention, that the Y element in the seedcrystals is selected from the group consisting of Si, Sn, Ti, Zr, Ge andcombinations of two or more thereof, wherein more preferably thetetravalent element Y comprises Si and/or Ti. More preferably, thetetravalent element Y in the seed crystals is Si.

According to step (i) of the present inventive process, one or moresources for B₂O₃ are comprised in mixture of said step. As to the one ormore sources for B₂O₃ which may be employed according to the inventiveprocess, again no particular restriction applies in their respectprovided that at least a portion of the B₂O₃ contained therein or whichmay be provided by said source by appropriate chemical transformationthereof may be incorporated into the MWW framework structure as B₂O₃.According to the present invention, said one or more sources for B₂O₃are preferably selected from the group consisting of boric acid, boronoxide, borates, borate esters, and combinations of two or more thereof,preferably selected from the group consisting of boric acid, boronoxide, orthoborates, diborates, triborates, tetraborates, trimethylborate, triethyl borate, and combinations of two or more thereof,wherein more preferably the one or more sources for B₂O₃ are boron oxideand/or boric acid. More preferably, boric acid is employed as the sourcefor B₂O₃ in the mixture of step (i).

As regards the amounts in which YO₂ and B₂O₃ may be employed in theinventive process, these may be used in any suitable amounts providedthat a boron-containing zeolitic material may be obtained according tothe inventive process in which both YO₂ and B₂O₃ are contained in theMWW framework structure of the resulting material. Thus, according topreferred embodiments of the present inventive process, the molar ratioYO₂:B₂O₃ of the one or more sources of YO₂ to the one or more sourcesfor B₂O₃ in the mixture prepared in (i) is in the range of from 1:1 to100:1, preferably from 1.2:1 to 50:1, more preferably from 1.5:1 to20:1, more preferably from 1.8:1 to 10:1, more preferably from 2:1 to5:1, and more preferably from 2.2:1 to 4:1. More preferably, the molarratio YO₂ :B₂O₃ of the one or more sources of YO₂ to the one or moresources for B₂O₃ in the mixture prepared in (i) is in the range of from2.5:1 to 3.5:1.

Concerning the seed crystals, in instances wherein the seed crystalscontain one or more zeolitis materials, there is no restriction as towhether said seed crystals contain an organotemplate or not, dependingon whether an organotemplate was employed in the preparation of the oneor more zeolitic materials. Therefore, the seed crystals can principallybe used in an uncalcined form which contains an organotemplate, or in acalcined form which does not contain organotemplates due to thecalcination conditions under which the organotemplates are burned out ofthe seed crystals.

According to the present inventive process, apart from the one or moreorganotemplates provided in (i), there is principally no restriction asto further organotemplates which may be contained in the mixtureprovided therein. Thus, any further suitable further organotemplate ororganotemplates may be prepared in (i), provided that a layer precursorof the boron-cotaining zeolitic material may be obtained in (ii) and azeolitic material having an MWW/framework structure may be obtained in(iii) after calcination thereof. Besides the addition of one or morefurther organotemplates as such, said one or more furtherorganotemplates may independently thereof also be provided via the seedcrystals. It is, however, preferred according to the present inventionthat apart from organotemplate optionally contained in the seedcrystals, the mixture provided according to step (i) does not containpiperidine or hexamethyleneimine, preferably does not contain bothpiperidine and hexamethyleneimine, and more preferably does not contain(C₄-C₇)alkyleneimines and (C₅-C₈)alkylamines other than the one or moreorganotemplates according to formula (I), and more preferably does notcontain alkyleneimines and alkylamines other than the one or moreorganotemplates according to formula (I). According to the presentinvention it is particularly preferred that the mixture provided in (i)does not contain any further organotemplates than the one or moreorganotemplates according to formula (I), including organotemplatesoptionally present in the seed crystals. Withing the meaning of thepresent invention, unless specified otherwise, the wording “does notcontain” with respect to components contained in the mixture prepared in(i) and crystallized in (ii) indicates an amount of 5 wt.-% or less ofsaid components based on 100 wt.-% of YO₂ contained in the mixtureprepared in (i) and crystallized in step (ii), and preferably an amountof 3 wt.-% or less , more preferably of 2 wt.-% or less, more preferablyof 1 wt.-% or less, more preferably of 0.5 wt.-% or less, morepreferably of 0.1 wt.-% or less, more preferably of 0.05 wt.-% or less,more preferably of 0.01 wt.-% or less, more preferably of 0.005 wt.-% orless, and more preferably of 0.001 wt.-% or less of said componentsbased on 100 wt.-% of YO₂ contained in the mixture prepared in (i) andcrystallized in step (ii).

Concerning the amount of the one or more organotemplates which may beemployed in the inventive process, no particular restriction appliessuch that any suitable amount may be used provided that aboron-containing zeolitic material having an MWW/framework structurecomprising YO₂ and B₂O₃ may be obtained. According to the presentinventive process, it is however preferred that the molar ratioorganotemplate:YO₂ of the one or more organotemplates to the one or moresources for YO₂ in the mixture prepared in (i) is in the range of from0.05:1 to 3:1, preferably from 0.1:1 to 1.5:1, more preferably from0.2:1 to 0.8:1, more preferably from 0.25:1 to 0.5:1, more preferablyfrom 0.3:1 to 0.4:1, more preferably from 0.32:1 to 0.35:1, morepreferably from 0.33:1 to 0.34:1, wherein the one or moreorganotemplates do not include organotemplate optionally contained inthe seed crystals, wherein said one or more sources for YO₂ may includeor not include the amount of YO₂ provided in the seed crystals in step(i), and preferably do not include the amount of YO₂ provided to themixture by the seed crystals in step (i).

According the present inventive process, it is further preferred thatthe molar ratio YO₂:B₂O₃: organotemplate of the one or more sources ofYO₂ to the one or more sources of B₂O₃ to the one or moreorganotemplates in the mixture provided according to step (i) is in therange of 1:(0.01-1):(0.05-3), preferably in the range of1:(0.02-0.8):(0.1-1.5), more preferably in the range of1:(0.05-0.7):(0.2-0.8), more preferably in the range of1:(0.1-0.6):(0.25-0.5), more preferably in the range of1:(0.2-0.5):(0.3-0.4), more preferably in the range of1:(0.25-0.45):(0.32-0.35), more preferably in the range of1:(0.3-0.4):(0.33-0.34), wherein the one or more organotemplates do notinclude the organotemplate optionally contained in the seed crystals,wherein said one or more sources for YO₂ may include or not include theamount of YO₂ provided by the seed crystals, wherein said one or moresources for B₂O₃ may include or not include the amount of B₂O₃ in theseed crystals when the seed crystals contain B₂O₃ in step (i). Accordingto the present invention, it is preferred that the one or more sourcesfor YO₂ do not include the amount of YO₂ provided to the mixture by theseed crystals in step (i), nor does the one or more sources of B₂O₃include the amount of B₂O₃ which may be contained in the seed crystalsin step (i).

In principle, there is no restriction as to further components which maybe prepared in (i) of the inventive process, provided that a layeredprecursor of the boron-containing zeolitic material may be obtained in(ii) and subsequently a boron-containing zeolitic material having an MWWframework structure may be obtained in (iii). Thus, by way of example,it is further preferred according to the present inventive process, thatthe mixture prepared in (i) comprises one or more sources for M₂O,wherein M stands for one or more alkali metals M. In this respect, theone or more alkali metals M are preferably selected from the groupconsisting of Li, Na, K, Rb, Cs, and combinations of two or morethereof, more preferably from the group consisting of Li, Na, Rb andcombinations of two or more thereof, wherein more preferably the one ormore alkali metals M are Li and/or Na. More preferably, the mixtureprepared in (i) of the present inventive process comprises one or moresources of Na₂O. Within the meaning of the present invention, the term“M₂O” does not refer to the oxide as such but, as for the terms “YO₂”and “X₂O₃” such as B₂O₃ to the presence of said compounds asconstituting elements of the framework structure of the zeoliticmaterial, wherein “M₂O” refers to M as extra-framework element which isionically bound to the negatively charged framework and which mayaccordingly be ion exchanged against one or more further cationicelements and/or moieties.

In instances wherein one or more sources for M₂O are provided in themixture in step (i), no particular restriction applies neither withrespect to the type or types of M, nor with respect to the amounts inwhich the one or more sources for M₂O may be provided. Thus, by way ofexample, the molar ratio M₂O:YO₂ of the mixture prepared in (i) mayrange anywhere from from 0.0005:1 to 2:1, preferably from 0.001:1 to1:1, more preferably from 0.005:1 to 0.5:1, more preferably from 0.01:1to 0.3:1, more preferably from 0.03:1 to 0.1:1, more preferably from0.05:1 to 0.08:1. More preferably, the molar ratio M₂O:YO₂ of themixture prepared in (i) is in the range of from 0.06:1 to 0.07:1.

Furthermore, it is preferred according to the inventive process that themolar ratio YO₂:B₂O₃ : M₂O of the mixture prepared in (i) is in therange of 1:(0.01-1):(0.0005-2), preferably in the range of1:(0.02-0.8):(0.001-1), more preferably in the range of1:(0.05-0.7):(0.005-0.5), more preferably in the range of1:(0.1-0.6):(0.01-0.3), more preferably in the range of1:(0.2-0.5):(0.03-0.1), and more preferably in the range of1:(0.25-0.45):(0.05-0.08). More preferably, the molar ratio YO₂:B₂O₃:M₂Oof the mixture prepared in (i) is in the range of1:(0.3-0.4):(0.06-0.07).

According to preferred embodiments of the present inventive process, norestriction applies as to the amount of seed crystals in the mixtureprepared in (i). Thus, by way of example, the amount of seed crystalsprovided in (i) may range anywhere from 0.05 to 25 weight-% based on 100weight-% of YO₂ in the one or more sources for YO₂, wherein preferablythe amount of seed crystals ranges from 0.1 to 20 weight-%, morepreferably from 0.2 to 15 weight-%, more preferably from 0.5 to 12weight-%, more preferably from 1 to 10 weight-%, more preferably from 3to 7 weight-%. More preferably, the amount of seed crystals in themixture prepared in (i) is in the range of from 4 to 6 weight-%.

Step (ii)

According to the present inventive process, the mixture obtained in step(i) is crystallized in step (ii), for obtaining a layered precursor of aboron-containing MWW-type zeolitic material.

Concerning the crystallization procedure of step (ii), said procedure ispreferred to involve heating of the mixture of step (i), wherein anysuitable temperature may be employed provided that a layered precursorof the boron-containing zeolitic material may be obtained in (ii). Thus,by way of example, the crystallization in (ii) may be conducted at atemperature in the range of from 80 to 250° C., preferably from 100 to230° C., more preferably from 130 to 210° C., more preferably from 150to 200° C., and more preferably from 170 to 190° C. More preferably, thecrystallization process of step (ii) involves heating of the mixture ofstep (i) at a temperature in the range from 175 to 185° C.

Regarding the pressure under which crystallization in step (ii) may beperformed, again no particular restriction applies provided that azeolitic material having an MWW framework structure comprising YO₂ andB₂O₃ may be obtained in step (ii). Thus, by way of example,crystallization in step (ii) may be performed under ambient pressuresuch as in an open system or may be performed at pressures elevatedrelative to ambient pressure, in particular in instances whereincrystallization in step (ii) involves heating of the mixture.Accordingly, crystallization in step (ii) may be preformed in an opensystem for obtaining a zeolitic material having an MWW frame-workstructure comprising YO₂ and B₂O₃, or may be crystallized at an elevatedpressure relative to ambient pressure either by artificially increasingthe pressure under which crystallization takes place and/or by creatingpressure in the mixture crystallized in step (ii) by means of chemicalreaction and/or physical heating of the mixture. According to theinventive process it is accordingly preferred that in step (ii) themixture is crystallized under autogenous pressure. To this effect,crystallization in step (ii) is preferably performed in a pressure-tightvessel, more preferably in an autoclave.

Concerning the duration of the crystallization procedure in step (ii),no specific restrictions exist. It is however preferred that saidprocedure is carried out for a period in the range of from 1 d to 25 d,preferably from 3 d to 20 d, more preferably from 5 d to 18 d, morepreferably from 7 d to 15 d, more preferably from 9 to 12 d. Morepreferably, the crystallization procedure in step (ii) is carried outfor a period in the range of from 9.5 to 10.5 d.

According to the present invention, it is preferred that after after(ii) and prior to (iii) the process further comprises

(a) isolating the layered precursor obtained in (ii), preferably byfiltration,

(b) optionally washing the layered precursor obtained in (a),

(c) optionally drying the layered precursor obtained in (a) or (b),

(d) optionally subjecting the layered precursor obtained in (a), (b), or(c) to ion exchange,

(e) optionally subjecting the layered precursor obtained in (a), (b),(c), or (d) to isomorphous substitution.

In step (a) of the inventive process, the layered precursor obtained instep (ii) may be isolated by any conceivable means, such as filtration,ultrafiltration, diafiltration, centrifugation, spray-drying and/ordecantation methods, wherein the filtration methods may involve suctionand/or pressure filtration steps. Preferably, the isolation of thelayered precursor obtained step (ii) is achieved by filtration and/orspray drying, more preferably by filtration.

In optional step (b) of the inventive process, the washing of thelayered precursor may be achieved by any conceivable means using anysuitable washing agents. Washing agents which may be used are, forexample, water, alcohols, and mixtures of two or more thereof. Morespecifically, the washing agents may be selected from the groupconsisting of water, methanol, ethanol, propanol, or mixtures of two ormore thereof. Examples of mixtures are mixtures of two or more alcohols,such as methanol and ethanol, or methanol and propanol, or ethanol andpropanol, or methanol and ethanol and propanol, or mixtures of water andat least one alcohol, such as water and methanol, or water and ethanol,or water and propanol, or water and methanol and ethanol, or water andmethanol and propanol, or water and methanol and ethanol and propanol.More preferably, the washing agents are water and/or at least onealcohol, more preferably water and/or ethanol. Even more preferably, thewashing agent is water in optional step (b).

In optional step (c) of the inventive process, the drying of the layeredprecursor may be achieved by any conceivable temperature, provided thatthe solvent residues and/or moisture comprised in the layered precursoris removed. Accordingly, said drying procedure may principally beachieved by any one of for example desiccation, freeze-drying, heating,and/or applying vacuum to the layered precursor obtained in step (a) or(b).

According to preferred embodiments, drying in step (c) is achieved byheating of the layered precursor to a temperature in the range of from50 to 250° C., preferably from 80 to 200° C., more preferably from 100to 150° C., more preferably from 110 to 130° C. In general, the dryingprocedure of optional step (c) is performed for a duration which allowsfor the substantial removal of any solvent and/or moisture from thelayered precursor. Preferably, drying is performed for a duration in therange of from 1 to 48 h, more preferably from 2 to 24 h, more preferablyfrom 5 to 16 h.

According to the present invention, the layered precursor obtained in(a), (b), or (c) is preferably subject in (d) to one or more ionexchange procedures with H⁺ and/or NH₄ ⁺, preferably with NH₄ ⁺.According to particularly preferred embodiments of the present inventionwherein the mixture prepared in (i) comprises one or more sources forM₂O, it is preferred that the one or more alkali metals M according toany of the particular and preferred embodiments of the present inventionand in particular Na is contained as exchangeable ions in the layeredprecursor obtained in (a), (b), or (c) and is accordingly exchanged in(d) against H⁺ and/or NH₄ ⁺, and preferably against NH₄ ⁺.

As regards the preferred ion exchange procedure in (d), it is furtherpreferred that said procedure is repeated at least once, wherein morepreferably the ion-exchange procedure in (d) is repeated from one tofive times, preferably from one to four times, and more preferably twoor three times. According to the present invention it is particularlypreferred that the ion exchange procedure in (d) of the layeredprecursor obtained in (a), (b), or (c) is repeated twice.

Concerning the temperature at which the preferred ion exchange procedurein (d) is conducted, again, no particular restrictions apply providedthat at least a portion of the exchangeable ions contained in thelayered precursor obtained in (a), (b), or (c) may be exchanged againstH⁺ and/or NH₄ ⁺, and preferably against NH₄ ⁺. Thus, by way of example,the ion-exchange procedure in (d) may conducted at a temperature in therange of anywhere from 30 to 160° C., wherein preferably the ionexchange procedure in (d) is conducted at a temperature in the range offrom 40 to 140° C., more preferably from 50 to 120° C., more preferablyfrom 60 to 100° C., more preferably from 70 to 90° C., and morepreferably of from 75 to 85° C.

According to the present invention it is preferred that the ion exchangeprocedure in (d) is conducted in a solvent system comprising one or moresolvents. As concerns the solvent system which may be employed to thiseffect, no particular restrictions apply such that in principle anysolvent system may be employed in (d), provided that at least a portionof the exchangeable ions contained in the layered precursor obtained in(a), (b), or (c) may be exchanged against H⁺ and/or NH₄ ⁺, andpreferably against NH₄ ⁺. Thus, by way of example, the solvent systemmay comprise water and/or one or more organic solvents, whereinpreferably one or more solvents comprised in the solvent system areselected from the group consisting of water, monohydric alcohols,polyhydric alcohols, and combinations of two or more thereof, morepreferably from the group consisting of water, methanol, ethanol,propanol, butanol, pentanol, ethane-1,2-diol, propane-1,2-diol,propane-1,2,3-triol, butane-1,2,3,4-tetraol, pentane-1,2,3,4,5-pentol,and combinations of two or more thereof, and more preferably from thegroup consisting of water, methanol, ethanol, 2-propanol, and mixturesof two or more thereof. According to the present invention, it isparticularly preferred that the solvent system preferably employed in(d) comprises water, wherein more preferably the ion-exchange procedureis conducted in water as the solvent system, more preferably indeionized water.

As regards the duration of the ion exchange, no particular restrictionsapply according to the present invention such that ion exchange may inprinciple be conducted for any suitable duration provided that at leasta portion of the exchangeable ions contained in the layered precursorobtained in (a), (b), or (c) may be exchanged against H⁺ and/or NH₄ ⁺,and preferably against NH₄ ⁺. Thus, by way of example, ion exchange in(d) may be conducted for a duration ranging anywhere from 15 min to 6 h,wherein preferably ion exchange in (d) is conducted for a durationranging from 30 min to 3 h, and more preferably from 45 min to 1.5 h.

In optional step (e) of the inventive process, boron in the frameworkstructure of the layered precursor obtained in (a), (b), (c), or (d) isisomorphously substituted against one or more trivalent and/ortetravalent elements. According to the present invention, no particularrestrictions apply as to the one or more trivalent and/or tetravalentelements which may be employed to this effect, provided that at least aportion of the boron contained in the framework structure of the layeredprecursor obtained in (a), (b), (c), or (d) is isomorphously substitutedagainst one or more of said elements. It is, however, preferredaccording to the inventive process that, independently from one another,the one or more trivalent elements are selected from the groupconsisting of Al, Ga, In, and combinations of two or more thereof, andthe one or more tetravalent elements are selected from the groupconsisting of Ti, Ge, Sn, and combinations of two or more thereof.According to the present invention it is however particularly preferredthat the layered precursor obtained in (a), (b), (c), or (d) isisomorphously substituted against Al and/or Ti, and preferably againstAl.

As regards the form in which the one of more trivalent and/ortetravalent elements for isomorphous substitution in optional step (e)are employed according to particular and preferred embodiments of thepresent invention, no particular restrictions apply provided that atleast a potion of the boron contained in the framework structure of thelayered precursor obtained in (a), (b), (c), or (d) is isomorphouslysubstituted against one or more of said elements. It is, however,preferred according to the inventive process that in (e) the one or moretrivalent and/or tetravalent elements for isomorphous substitution areprovided in the form of one or more salts, and preferably in the form ofone or more salts selected from the group consisting of halides,sulfates, sulfites, hydroxides, nitrates, nitrites, phosphates,phosphites, acetates, and mixtures of two or more thereof, morepreferably in the form of one or more salts selected from the groupconsisting of chlorides, bromides, sulfates, hydroxides, nitrates,phosphates, acetates, and mixtures of two or more thereof. According tothe present invention it is particularly preferred that the one or moretrivalent and/or tetravalent elements for isomorphous substitution in(e) are provided in the form of their nitrates.

According to the present invention it is preferred that the isomorphoussubstitution in (e) is conducted in a solvent system comprising one ormore solvents. As concerns the solvent system which may be employed tothis effect, no particular restrictions apply such that in principle anysolvent system may be employed in (e), provided that at least a potionof the boron contained in the framework structure of the layeredprecursor obtained in (a), (b), (c), or (d) is isomorphously substitutedagainst one or more of the trivalent and/or tetravalent elements. Thus,by way of example, the solvent system may comprise water and/or one ormore organic solvents, wherein preferably one or more solvents comprisedin the solvent system are selected from the group consisting of water,monohydric alcohols, polyhydric alcohols, and combinations of two ormore thereof, more preferably from the group consisting of water,methanol, ethanol, propanol, butanol, pentanol, ethane-1,2-diol,propane-1,2-diol, propane-1,2,3-triol, butane-1,2,3,4-tetraol,pentane-1,2,3,4,5-pentol, and combinations of two or more thereof, andmore preferably from the group consisting of water, methanol, ethanol,2-propanol, and mixtures of two or more thereof. According to thepresent invention, it is particularly preferred that the solvent systempreferably employed in (e) comprises water, wherein more preferably theion-exchange procedure is conducted in water as the solvent system, morepreferably in deionized water.

As regards the duration of the isomorphous substitution in (e), noparticular restrictions apply according to the present invention suchthat isomorphous substitution may in principle be conducted for anysuitable duration provided that at least a portion of the boroncontained in the framework structure of the layered precursor obtainedin (a), (b), (c), or (d) is isomorphously substituted against one ormore of the trivalent and/or tetravalent elements. Thus, by way ofexample, isomorphous substitution in (e) may be conducted for a durationranging anywhere from 0.5 to 10 d, wherein preferably isomorphoussubstitution in (e) is conducted for a duration ranging from 1 to 8 d,more preferably from 2 to 6 d, more preferably from 2.5 to 5.5 d, morepreferably from 3 to 5 d, and more preferably from 3.5 to 4.5 d.

Concerning the temperature at which the isomorphous substitution in (e)is conducted, again, no particular restrictions apply provided that atleast a portion of the boron contained in the framework structure of thelayered precursor obtained in (a), (b), (c), or (d) is isomorphouslysubstituted against one or more of the trivalent and/or tetravalentelements. Thus, by way of example, the isomorphous substitution in (e)may conducted at a temperature in the range of anywhere from 30 to 160°C., wherein preferably the isomorphous substitution in (e) is conductedat a temperature in the range of from 50 to 140° C., more preferablyfrom 70 to 120° C., more preferably from 90 to 110° C., and morepreferably from 95 to 105° C.

Step (iii)

According to the present inventive process, the layered precursorobtained in step (ii) is calcined for obtaining a boron-containingzeolitic material having an MWW framework structure.

Concerning the calcination procedure in step (iii), no particularrestriction applies, provided that a boron-containing zeolitic materialhaving an MWW framework structure is obtained in (iii). Thus,calcination may be performed under any suitable conditions, wherein saidprocess is preferably carried out at a temperature in the range of from300 to 900° C., preferably from 400 to 700° C., more preferably from 450to 650° C. More preferably, the calcination procedure in step (iii) iscarried out at a temperature from 500 to 600° C.

According to preferred embodiments of the present invention, theinventive process may further comprise after (iii) one or more steps of

(iv) deboronating the zeolitic material having an MWW frameworkstructure obtained in (iii) with a liquid solvent system, therebyobtaining a deboronated zeolitic material having an MWW frameworkstructure.

The deboronation procedure of the present invention relates to aprocedure wherein at least a portion of the boron atoms contained in thezeolitic framework structure is removed. Within the meaning of thepresent invention, deboronation preferably does not lead to a completeremoval of the boron contained in the framework structure but only to areduction of its content such that in any case at least traces of boronwill remain in the framework after completion of the deboronationprocedure.

The liquid solvent system used in step (iv) is preferably selected fromthe group consisting of water, monohydric alcohols, polyhydric alcohols,and mixtures of two or more thereof. Concerning the monohydric alcoholsand polyhydric alcohols, no specific restrictions exist. Preferably,these alcohols contain from 1 to 6 carbon atoms, more preferably from 1to 5 carbon atoms, more preferably from 1 to 4 carbon atoms, and morepreferably from 1 to 3 carbon atoms. The polyhydric alcohols preferablycomprise from 2 to 5 hydroxyl groups, more preferably from 2 to 4hydroxyl groups, preferably 2 or 3 hydroxyl groups. Especially preferredmonohydric alcohols are methanol, ethanol, and propanol like 1-propanoland 2-propanol. Especially preferred polyhydric alcohols areethane-1,2-diol, propane-1,2-diol, propane-1,3-diol,propane-1,2,3-triol. If mixtures of two or more of above-describedcompounds are employed, it is preferred that these mixtures comprisewater and at least one monohydric and/or at least one polyhydricalcohol. Even more preferably, the liquid solvent system consists ofwater.

As regards the liquid solvent system used for the deboronation procedureof step (iv), in principle no particular restriction applies withrespect to further components which may be contained in said liquidsolvent system in addition to the particular and preferred solvents andcombinations of solvent and in particular water which is particularlypreferred as the solvent system. It is, however, preferred according tothe present invention that the liquid solvent system does not contain aninorganic or organic acid or a salt thereof, the acid being selectedfrom the group consisting of hydrochloric acid, sulfuric acid, nitricacid, phosphoric acid, formic acid, propionic acid, oxalic acid, andtartaric acid. According to the present invention it is furtherpreferred that the solvent system used for the deboronation proceduredoes not contain an inorganic or organic acid or a salt thereof, whereineven more preferably the solvent system used for the deboronationprocedure consists of water such that it does not contain any furthercomponents other than possible traces of impurities which may be presentin distilled water.

As far as the amount of boron-containing zeolite relative to the amountof liquid solvent system for the deboronation procedure of step (iv), nospecific restrictions exist. Preferably, the weight ratio of theboron-containing zeolitic material having an MWW/ framework structurerelative to the liquid solvent system is in the range of from 1:5 to1:40, more preferably from 1:10 to 1:30, more preferably from 1:10 to1:20 such as from 1:10 to 1:15, from 1:11 to 1:16, from 1:12 to 1:17,from 1:13 to 1:18, from 1:14 to 1:19, from 1:15 to 1:20.

Concerning the deboronation procedure in step (iv), said process ispreferably carried out at a temperature in the range of from 50 to 125°C., more preferably from 70 to 120° C., more preferably from 90 to 115°C., more preferably from 90 to 110° C., more preferably from 95 to 105°C. More preferably, the deboronation according to step (iv) is carriedout at the boiling point of the solvent system. If the solvent systemcomprises 2 or more components, the deboronation according to step (iv)is preferably carried out at the boiling point of the component havingthe lowest boiling point. According to a further preferred embodiment ofthe present invention, the deboronation according to step (iv) iscarried out under reflux. Thus, the preferred vessel used for thedeboronation according to step (iv) is equipped with a reflux condenser.During the deboronation procedure of step (iv), the temperature of theliquid solvent system is kept essentially constant or changed. Morepreferably, the temperature is kept essentially constant.

Concerning the duration of the deboronation procedure in step (iv), nospecific restrictions exist. Preferably, said deboronation procedure iscarried out for a time period in the range of from 6 to 20 h, preferablyfrom 7 to 17 h, more preferably from 8 to 14 h. More preferably, thedeboronation procedure in step (iv) is carried out at a time period inthe range of from 9 to 12 h. The time period is to be understood as thetime where the liquid solvent system is maintained under theabove-described deboronation temperature.

In principle, no particular restrictions apply relative to the seedcrystals which may be employed in (i) provided that obtaining a layeredprecursor of the MWW framework structure may be obtained in (ii), fromwhich a zeolitic material having an MWW framework structure may beobtained in (iii). According to the present invention, it is preferredthat the seed crystals in the mixture prepared in (i) comprise azeolitic material having an MWW framework structure and/or a layeredprecursor of a zeolitic material having an MWW framework structure. Morepreferably, the seed crystals comprise a zeolitic material having an MWWframework structure which is obtained or obtainable according to thepresent inventive process, and/or a layered precursor which is obtainedor obtainable according to step (ii) of the present inventive process.Even more preferably, the seed crystals comprise a layered precursorwhich is obtained or obtainable according to step (ii) of the presentinventive process.

As regards particular and preferred embodiments of the present inventionwherein the seed crystals comprise a layered precursor of a zeoliticmaterial having an MWW framework structure, it is further preferredaccording to the present invention that the layered precursor isselected from the group consisting of MCM-22(P), [Ga—Si—O]-MWW(P),[Ti—Si—O]-MWW(P), ERB-1(P), ITQ-1(P), PSH-3(P), SSZ-25(P), and mixturesof two or more thereof, wherein the layered precursor is more preferablyselected from the group consisting of MCM-22(P), ITQ-1(P), SSZ-25(P),and mixtures of two or more thereof. According to the inventive processit is particularly preferred that the layered precursor of the preferredseed crystals comprises MCM-22(P) and/or SSZ-25(P), preferablyMCM-22(P), wherein more preferably MCM-22(P) is employed as the seedcrystals in the mixture prepared in (i) and crystallized in (ii).

On the other hand, concerning particular and preferred embodiments ofthe present invention wherein the seed crystals comprise a zeoliticmaterial having an MWW framework structure, it is further preferredaccording to the present invention that the zeolitic material isselected from the group consisting of MCM-22, [Ga—Si—O]-MWW,[Ti—Si—O]-MWW, ERB-1, ITQ-1, PSH-3, SSZ-25, and mixtures of two or morethereof, wherein the zeolitic material is more preferably selected fromthe group consisting of MCM-22, ITQ-1, SSZ-25, and mixtures of two ormore thereof. According to the inventive process it is particularlypreferred that the zeolitic material of the preferred seed crystalscomprises MCM-22 and/or SSZ-25, preferably MCM-22, wherein morepreferably MCM-22 is employed as the seed crystals in the mixtureprepared in (i) and crystallized in (ii).

Within the meaning of the present invention and unless stated otherwise,the compounds designated as “MCM-22”, “ERB-1”, “ITQ-1”, “PSH-3”, and“SSZ-25” respectively stand for the Al-containing form thereof, i.e.Al-MCM-22, Al-ERB-1, Al-ITQ-1, Al-PSH-3, and Al-SSZ-25, respectively.Same applies according relative to the respective layered precursorthereof which, unless stated otherwise, stands for the Al-containingform, i.e. for Al-MCM-22(P), Al-ERB-1(P), Al-ITQ-1(P), Al-PSH-3(P), andAl-SSZ-25(P), respectively.

Concerning the state in which the mixture prepared in (i) is providedfor crystallization in step (ii), no particular restriction appliesprovided that a zeolitic material having an MWW framework structurecomprising YO₂ and B₂O₃ may be obtained, such that any grade ofadmixture may in principle be employed to this effect. It is, however,preferred according to the inventive process that in addition to theadmixing of the one or more sources for YO₂, one or more sources forB₂O₃, one or more organotemplates, and seed crystals, the mixture isfurther homogenized prior to the crystallization in step (ii). Accordingto the inventive process, said preferred homogenization may be achievedby a further mixing step prior to the crystallization in step (ii),wherein preferably said additional mixing includes the grinding and/ormilling of the mixture prepared in (i) wherein more preferably themixture prepared in (i) is homogenized by milling thereof prior to thecrystallization in step (ii).

In addition to relating to a process for the preparation of a zeoliticmaterial having an MWW framework structure comprising YO₂ and B₂O₃ thepresent invention further relates to the zeolitic material having an MWWframework structure comprising YO₂ and B₂O₃ as said material is obtainedaccording to any of the particular and preferred embodiments of theinventive process as described in the present application. Furthermore,the present invention also relates to a zeolitic material having an MWWframework structure comprising YO₂ and B₂O₃ as it may be obtained, i.e.as obtainable, according to any of the particular and preferredembodiments of the inventive process as described herein. In particular,the present invention further relates to a zeolitic material having anMWW framework structure comprising YO₂ and B₂O₃ as said material may beobtained according to the inventive process, yet independently of themethod according to which it has actually been prepared or obtained suchthat the zeolitic material having an MWW framework structure comprisingYO₂ and B₂O₃ which is obtainable according to the inventive process isnot limited to materials having directly been obtained by said process.

Concerning the synthetic boron-containing zeolitic materials of thepresent invention, no particular restrictions apply relative to theirchemical and physical properties provided that they may be obtainedaccording to any of the particular or preferred embodiments of thepresent invention as defined in the present application. This alsoapplies with respect to the structure of the inventive materials, suchthat no particular restrictions apply in this respect, provided that thematerial displays the MWW framework structure.

Applications

The present invention further relates to the use of the aforementionedboron-containing zeolitic material having an MWW framework structure.

In principle, the inventive materials may be used in any suitableapplication. Thus, by way of example the synthetic boron-containingzeolitic material according to any of the particular and preferredembodiments of the present invention may be used as a precursor forfurther structural modification, as a catalyst, as a catalyst support,as an adsorbent, as a filler, and/or as a molecular sieve. Preferably,the inventive zeolitic material is used as a molecular sieve, as anadsorbent, more preferably for ion-exchange and/or for separation of gasor liquid mixtures, as a catalyst and/or as a catalyst component, morepreferably for hydrocarbon conversion, dehydration, epoxidation, epoxidering opening, etherification, esterification, ammoxidation, or dieseloxidation catalysis, and more preferably for isomerization, alkylation,or epoxidation. According to the present invention it is particularlypreferred that the zeolitic material having an MWW framework structureis used as a catalyst for epoxidation or alkylation, and more preferablyfor epoxidation. According to the present invention it is furtherparticularly preferred that the zeolitic material having an MWWframework structure as obtainable and/or obtained according to any ofthe particular and preferred embodiments of the inventive process isused as a catalyst for the epoxidation of propylene to propylene oxide.

The present invention is further characterized by the followingpreferred embodiments, including the combinations of embodimentsindicated by the respective dependencies:

-   -   1. A process for the production of a zeolitic material having an        MWW framework structure comprising YO₂ and B₂O₃, wherein Y        stands for a tetravalent element, said process comprising        -   (i) preparing a mixture comprising one or more sources for            YO₂, one or more sources for B₂O₃, one or more            organotemplates, and seed crystals,        -   (ii) crystallizing the mixture obtained in (i) for obtaining            a layered precursor of the MWW framework structure,        -   (iii) calcining the layered precursor obtained in (ii) for            obtaining the zeolitic material having an MWW/ framework            structure,        -   wherein the one or more organotemplates have the formula (I)

R¹ R²R³N   (I)

-   -   -   wherein R¹ is (C₅-C₈)cycloalkyl, and        -   wherein R² and R³ are independently from each other H or            alkyl, and        -   wherein the mixture prepared in (i) and crystallized in (ii)            contains 35 wt.-% or less of H₂O based on 100 wt.-% of YO₂            contained in the mixture prepared in (i) and crystallized in            (ii), preferably 30 wt.-% or less, more preferably 25 wt.-%            or less, more preferably 20wt.-% or less, more preferably 25            wt.-% or less, more preferably 10 wt.-% or less, more            preferably 5 wt.-% or less, more preferably 3 wt.-% or less,            more preferably 1 wt.-% or less, more preferably 0.5 wt.-%            or less, more preferably 0.1 wt.-% or less, more preferably            0.05 wt.-% or less, and more preferably 0.01 wt.-% or less            based on 100 wt.-% of YO₂.

    -   2. The process of embodiment 1, wherein the mixture prepared        in (i) and crystallized in (ii) contains 5 wt.-% or less of        fluoride calculated as the element and based on 100 wt.-% of        YO₂, preferably 3 wt.-% or less, more preferably 2 wt.-% or        less, more preferably 1 wt.-% or less, more preferably 0.5 wt.-%        or less, more preferably 0.1 wt.-% or less, more preferably 0.05        wt.-% or less, more preferably 0.01 wt.-% or less, more        preferably 0.005 wt.-% or less, and more preferably 0.001 wt.-%        or less or fluoride calculated as the element and based on 100        wt.-% of YO₂.

    -   3. The process of embodiment 1 or 2, wherein the mixture        prepared in (i) and crystallized in (ii) contains 5 wt.-% or        less of P and/or Al calculated as the respective element and        based on 100 wt.-% of YO₂, preferably 3 wt.-% or less, more        preferably 2 wt.-% or less, more preferably 1 wt.-% or less,        more preferably 0.5 wt.-% or less, more preferably 0.1 wt.-% or        less, more preferably 0.05 wt.-% or less, more preferably 0.01        wt.-% or less, more preferably 0.005 wt.-% or less, more        preferably 0.001 wt.-% or less of P and/or Al calculated as the        respective element and based on 100 wt.-% of YO₂.

    -   4. The process of any of embodiments 1 to 3, wherein the layered        precursor obtained in (ii) is selected from the group consisting        of B-MCM-22(P), B-ERB-1(P), B-ITQ-1(P), B-PSH-3(P), B-SSZ-25(P),        and mixtures of two or more thereof, preferably from the group        consisting of B-MCM-22(P), B-ITQ-1(P), B-SSZ-25(P), and mixtures        of two or more thereof, wherein more preferably the layered        precursor comprises B-MCM-22(P) and/or B-SSZ-25(P), preferably        B-MCM-22(P), and wherein more preferably the layered precursor        obtained in (ii) is B-MCM-22(P).

    -   5. The process of any of embodiments 1 to 4, wherein the        zeolitic material having an MWW framework structure obtained        in (iii) is selected from the group consisting of B-MCM-22,        B-ERB-1, B-ITQ-1, B-PSH-3, B-SSZ-25, and mixtures of two or more        thereof, preferably from the group consisting of B-MCM-22,        B-ITQ-1, B-SSZ-25, and mixtures of two or more thereof, wherein        more preferably the zeolitic material having an MWW framework        structure comprises B-MCM-22 and/or B-SSZ-25, preferably        B-MCM-22, and wherein more preferably the zeolitic material        having an MWW framework structure obtained in (iii) is B-MCM-22.

    -   6. The process of any of embodiments 1 to 5, wherein Y is        selected from the group consisting of Si, Sn, Ti, Zr, Ge, and        combinations of two or more thereof, Y preferably being Si        and/or Ti, wherein more preferably Y is Si.

    -   7. The process of any of embodiments 1 to 6, wherein the one or        more sources for YO₂ comprises one or more compounds selected        from the group consisting of silicas, silicates, silicic acid        and combinations of two or more thereof, preferably selected        from the group consisting of silicas, alkali metal silicates,        silicic acid, and combinations of two or more thereof, more        preferably selected from the group consisting of fumed silica,        colloidal silica, reactive amorphous solid silica, silica gel,        pyrogenic silica, lithium silicates, sodium silicates, potassium        silicates, silicic acid, and combinations of two or more        thereof, more preferably selected from the group consisting of        fumed silica, silica gel, pyrogenic silica, sodium silicates,        silicic acid, and combinations of two or more thereof, more        preferably selected from the group consisting of fumed silica,        silica gel, pyrogenic silica, and combinetions of two or more        thereof, wherein more preferably the one or more sources for YO₂        is silica gel, preferably silica gel of the formula SiO₂. x H₂O,        wherein x is in the range of from 0.1 to 1.165, preferably from        0.3 to 1.155, more preferably from 0.5 to 1.15, more preferably        from 0.8 to 1.13, and more preferably from 1 to 1.1.

    -   8. The process of any of embodiments 1 to 7, wherein R¹ is        selected from the group consisting of substituted and/or        unsubstituted cyclopentyl, cyclohexyl, cycloheptyl, and        cyclooctyl, more preferably from the group consisting of        substituted and/or unsubstituted cyclopentyl, cyclohexyl and        cycloheptyl, wherein more preferably R¹ is substituted or        unsubstituted cyclohexyl or cycloheptyl, more preferably        substituted or unsubstituted cyclohexyl, and more preferably        unsubstituted cyclohexyl.

    -   9. The process of any of embodiments 1 to 8, wherein R² and R³        are independently from each other H or (Ci-C3) alkyl, wherein        more preferably R² and R³ are independently from each other        selected from the group consisting of H, methyl, ethyl and        propyl, wherein more preferably R² and R³ are H.

    -   10. The process of any of embodiments 1 to 9, wherein the seed        crystals comprise YO₂ and X₂O₃, wherein X is a trivalent        element, wherein independently from one another X is preferably        selected from the group consisting of Al, B, In, Ga, and        combinations of two or more thereof, X more preferably being Al        and/or B, wherein more preferably X is Al, and Y is preferably        selected from the group consisting of Si, Sn, Ti, Zr, Ge, and        combinations of two or more thereof, Y more preferably being Si        and/or Ti, wherein more preferably Y is Si.

    -   11. The process of any of embodiments 1 to 10, wherein the one        or more sources for B₂O₃ are selected from the group consisting        of boric acid, boron oxide, borates, borate esters, and        combinations of two or more thereof, preferably selected from        the group consisting of boric acid, boron oxide, orthoborates,        diborates, triborates, tetraborates, trimethyl borate, triethyl        borate, and combinations of two or more thereof, wherein more        preferably the one or more sources for B₂O₃ are boron oxide        and/or boric acid, more preferably boric acid.

    -   12. The process of any of embodiments 1 to 11, wherein the molar        ratio YO₂:B₂O₃ of the one or more sources of YO₂ to the one or        more sources for B₂O₃ in the mixture prepared in (i) is in the        range of from 1:1 to 100:1, preferably from 1.2:1 to 50:1, more        preferably from 1.5:1 to 20:1, more preferably from 1.8:1 to        10:1, more preferably from 2:1 to 5:1, more preferably from        2.2:1 to 4:1, more preferably from 2.5:1 to 3.5:1.

    -   13. The process of any of embodiments 1 to 12, wherein the one        or more organotemplates are selected from the group consisting        of substituted and/or unsubstituted (C₅-C₈)cycloalkylamines,        preferably selected from the group consisting of substituted        and/or unsubstituted cyclopentylamine, cyclohexylamine,        cycloheptylamine, cyclooctylamine, and combinations of two or        more thereof, wherein more preferably the one or more        organotemplates are substituted and/or unsubstituted        cyclohexylamine and/or cycloheptylamine, more preferably        unsubstituted cyclohexylamine.

    -   14. The process of any of embodiments 1 to 13, wherein apart        from organotemplate optionally contained in the seed crystals,        the mixture prepared in (i) does not contain piperidine or        hexamethyleneimine, preferably does not contain piperidine and        hexamethyleneimine, more preferably does not contain        (C₄-C₇)alkyleneimines and (C₅-C₈)alkylamines other than the one        or more organotemplates according to formula (I), and more        preferably does not contain alkyleneimines and alkylamines other        than the one or more organotemplates according to formula (I).

    -   15. The process of any of embodiments 1 to 14, wherein the molar        ratio organotemplate: YO₂ of the one or more organotemplates to        the one or more sources for YO₂ in the mixture prepared in (i)        is in the range of from 0.05:1 to 3:1, preferably from 0.1:1 to        1.5:1, more preferably from 0.2:1 to 0.8:1, more preferably from        0.25:1 to 0.5:1, more preferably from 0.3:1 to 0.4:1, more        preferably from 0.32:1 to 0.35:1, more preferably from 0.33:1 to        0.34:1, wherein the one or more organotemplates do not include        organotemplate optionally contained in the seed crystals.

    -   16. The process of any of embodiments 1 to 15, wherein the molar        ratio YO₂:B₂O₃:organotemplate of the one or more sources of YO₂        to the one or more sources of B₂O₃ to the one or more        organotemplates in the mixture prepared in (i) is in the range        of 1:(0.01-1):(0.05-3), preferably in the range of        1:(0.02-0.8):(0.1-1.5), more preferably in the range of        1:(0.05-0.7):(0.2-0.8), more preferably in the range of        1:(0.1-0.6):(0.25-0.5), more preferably in the range of        1:(0.2-0.5):(0.3-0.4), more preferably in the range of        1:(0.25-0.45):(0.32-0.35), more preferably in the range of        1:(0.3-0.4):(0.33-0.34), wherein the one or more organotemplates        do not include organotemplate optionally contained in the seed        crystals.

    -   17. The process of any of embodiments 1 to 16, wherein the        mixture prepared in (i) comprises one or more sources for M₂O,        wherein M stands for one or more alkali metals M, wherein the        one or more alkali metals M are preferably selected from the        group consisting of Li, Na, K, Rb, Cs, and combinations of two        or more thereof, more preferably from the group consisting of        Li, Na, Rb and combinations of two or more thereof, wherein more        preferably the one or more alkali metals M are Li and/or Na,        more preferably Na.

    -   18. The process of embodiment 17, wherein the molar ratio        M20:YO₂ of the mixture prepared in (i) is in the range of from        0.0005:1 to 2:1, preferably from 0.001:1 to 1:1, more preferably        from 0.005:1 to 0.5:1, more preferably from 0.01:1 to 0.3:1,        more preferably from 0.03:1 to 0.1:1, more preferably from        0.05:1 to 0.08:1, more preferably from 0.06:1 to 0.07:1.

    -   19. The process of embodiment 17 or 18, wherein the molar ratio        YO₂:B₂O₃:M₂O of the mixture prepared in (i) is in the range of        1:(0.01-1):(0.0005-2), preferably in the range of        1:(0.02-0.8):(0.001-1), more preferably in the range of        1:(0.05-0.7):(0.005-0.5), more preferably in the range of        1:(0.1-0.6):(0.01-0.3), more preferably in the range of        1:(0.2-0.5):(0.03-0.1), more preferably in the range of        1:(0.25-0.45):(0.05-0.08), more preferably in the range of        1:(0.3-0.4):(0.06-0.07).

    -   20. The process of any of embodiments 1 to 19, wherein the        amount of seed crystals in the mixture prepared in (i) is in the        range of from 0.05 to 25 weight-% based on 100 weight-% of YO₂        in the one or more sources for YO₂, preferably from 0.1 to 20        weight-%, more preferably from 0.2 to 15 weight-%, more        preferably from 0.5 to 12 weight-%, more preferably from 1 to 10        weight-%, more preferably from 3 to 7 weight-%, more preferably        from 4 to 6 weight-%.

    -   21. The process of any of embodiments 1 to 20, wherein the        crystallization in (ii) involves heating of the mixture,        preferably at a temperature in the range of from 80 to 250° C.,        preferably from 100 to 230° C., more preferably from 130 to 210°        C., more preferably from 150 to 200° C., more preferably from        170 to 190° C., more preferably from 175 to 185° C.

    -   22. The process of any of embodiments 1 to 21, wherein the        crystallization in (ii) is conducted under autogenous pressure,        wherein crystallization in (ii) is preferably performed in a        pressure tight vessel, preferably in an autoclave.

    -   23. The process of any of embodiments 1 to 22, wherein the        crystallization in (ii) is carried out for a period in the range        of from 1 d to 25 d, preferably from 3 d to 20 d, more        preferably from 5 d to 18 d, more preferably from 7 d to 15 d,        more preferably from 9 to 12 d, more preferably from 9.5 to 10.5        d.

    -   24. The process of any of embodiments 1 to 23, wherein        after (ii) and prior to (iii) the process further comprises        -   (a) isolating the layered precursor obtained in (ii),            preferably by filtration,        -   (b) optionally washing the layered precursor obtained in            (a),        -   (c) optionally drying the layered precursor obtained in (a)            or (b),        -   (d) optionally subjecting the layered precursor obtained in            (a), (b), or (c) to ion exchange,        -   (e) optionally subjecting the layered precursor obtained in            (a), (b), (c), or (d) to isomorphous substitution.

    -   25. The process of embodiment 24, wherein in (d) the layered        precursor obtained in (a), (b), or (c) is subject to one or more        ion exchange procedures with H⁺ and/or NH₄ ⁺, preferably with        NH₄.

    -   26. The process of embodiment 24 or 25, wherein in (d) the ion        exchange procedure is repeated from one to five times,        preferably from one to four times, more preferably two or three        times, wherein more preferably the ion exchange procedure is        repeated twice.

    -   27. The process of any of embodiments 24 to 26, wherein in (d)        the ion exchange procedure is conducted at a temperature in the        range of from 30 to 160° C., preferably from 40 to 140° C., more        preferably from 50 to 120° C., more preferably from 60 to 100°        C., more preferably from 70 to 90° C., and more preferably from        75 to 85° C.

    -   28. The process of any of embodiments 24 to 27, wherein in (d)        the ion exchange procedure is conducted in a solvent system        comprising one or more solvents, wherein the one or more        solvents preferably comprise water and/or one or more organic        solvents, more preferably one or more solvents selected from the        group consisting of water, monohydric alcohols, polyhydric        alcohols, and combinations of two or more thereof, more        preferably selected from the group consisting of water,        methanol, ethanol, propanol, butanol, pentanol, ethane-1,2-diol,        propane-1,2-diol, propane-1,2,3-triol, butane-1,2,3,4-tetraol,        pentane-1,2,3,4,5-pentol, and combinations of two or more        thereof, more preferably selected from the group consisting of        water, methanol, ethanol, 2-propanol, and mixtures of two or        more thereof, wherein more preferably the one or more solvents        comprise water, wherein more preferably the ion exchange        procedure is conducted in water as the solvent system, more        preferably in deionized water.

    -   29. The process of any of embodiments 24 to 28, wherein in (d)        the ion exchange is conducted for a duration ranging from 15 min        to 6 h, preferably from 30 min to 3 h, and more preferably from        45 min to 1.5 h.

    -   30. The process of any of embodiments 24 to 29, wherein in (e)        boron in the framework structure of the layered precursor        obtained in (a), (b), (c), or (d) is isomorphously substituted        against one or more trivalent and/or tetravalent elements,        wherein independently from one another the one or more trivalent        elements are preferably selected from the group consisting of        Al, Ga, In, and combinations of two or more thereof, and the one        or more tetravalent elements are preferably selected from the        group consisting of Ti, Ge, Sn, and combinations of two or more        thereof, wherein more preferably the layered precursor obtained        in (a), (b), (c), or (d) is isomorphously substituted against Al        and/or Ti, preferably against Al.

    -   31. The process of any of embodiments 24 to 30, wherein in (e)        the one or more trivalent and/or tetravalent elements for        isomorphous substitution are provided in the form of one or more        salts, preferably in the form of one or more salts selected from        the group consisting of halides, sulfates, sulfites, hydroxides,        nitrates, nitrites, phosphates, phosphites, acetates, and        mixtures of two or more thereof, more preferably in the form of        one or more salts selected from the group consisting of        chlorides, bromides, sulfates, hydroxides, nitrates, phosphates,        acetates, and mixtures of two or more thereof, wherein more        preferably the one or more trivalent and/or tetravalent elements        for isomorphous substitution are provided in the form of their        nitrates.

    -   32. The process of any of embodiments 24 to 31, wherein in (e)        isomorphous substitution is conducted in a solvent system        comprising one or more solvents, wherein the one or more        solvents preferably comprise water and/or one or more organic        solvents, more preferably one or more solvents selected from the        group consisting of water, monohydric alcohols, polyhydric        alcohols, and combinations of two or more thereof, more        preferably selected from the group consisting of water,        methanol, ethanol, propanol, butanol, pentanol, ethane-1,2-diol,        propane-1,2-diol, propane-1,2,3-triol, butane-1,2,3,4-tetraol,        pentane-1,2,3,4,5-pentol, and combinations of two or more        thereof, more preferably selected from the group consisting of        water, methanol, ethanol, 2-propanol, and mixtures of two or        more thereof, wherein more preferably the one or more solvents        comprise water, wherein more preferably isomorphous        substitutions is conducted in water as the solvent system, more        preferably in deionized water.

    -   33. The process of any of embodiments 24 to 32, wherein in (e)        isomorphous substitution is conducted for a duration ranging        from 0.5 to 10 d, preferably from 1 to 8 d, more preferably from        2 to 6 d, more preferably from 2.5 to 5.5 d, more preferably        from 3 to 5 d, and more preferably from 3.5 to 4.5 d.

    -   34. The process of any of embodiments 24 to 33, wherein in (d)        the ion exchange procedure is conducted at a temperature in the        range of from 30 to 160° C., preferably from 50 to 140° C., more        preferably from 70 to 120° C., more preferably from 90 to 110°        C., and more preferably from 95 to 105° C.

    -   35. The process of any of embodiments 1 to 34, wherein the        calcination in (iii) is carried out at a temperature in the        range of from 300 to 900° C., preferably from 400 to 700° C.,        more preferably from 450 to 650° C., more preferably from 500 to        600° C.

    -   36. The process of any of embodiments 1 to 35, wherein        after (iii) the process further comprises        -   (iv) deboronating the zeolitic material having an MWW            framework structure obtained in        -   (iii) with a liquid solvent system, thereby obtaining a            deboronated zeolitic material having an MWW framework            structure.

    -   37. The process of embodiment 36, wherein the liquid solvent        system in (iv) is selected from the group consisting of water,        monohydric alcohols, polyhydric alcohols, and mixtures of two or        more thereof, and wherein said liquid solvent system does not        contain an inorganic or organic acid or a salt thereof, the acid        being selected from the group consisting of hydrochloric acid,        sulfuric acid, nitric acid, phosphoric acid, formic acid,        propionic acid, oxalic acid, and tartaric acid.

    -   38. The process of embodiment 36 or 37, wherein the deboronation        in (iv) is carried out at a temperature in the range of from 50        to 125° C., preferably from 70 to 120° C., more preferably from        90 to 115° C., more preferably from 90 to 110° C.

    -   39. The process of any of embodiments 36 to 38, wherein the        deboronation in (iv) is carried out for a time period in the        range of from 6 to 20 h, preferably from 7 to 17 h, more        preferably from 8 to 14 h, more preferably from 9 to 12 h.

    -   40. The process of any of embodiments 1 to 39, wherein the seed        crystals comprise a layered precursor of a zeolitic material        having an MWW framework structure, wherein the layered precursor        is preferably selected from the group consisting of MCM-22(P),        [Ga—Si—O]-MWW(P), [Ti—Si—O]-MWW(P), ERB-1(P), ITQ-1(P),        PSH-3(P), SSZ-25(P), and mixtures of two or more thereof,        -   wherein the layered precursor is more preferably selected            from the group consisting of MCM-22(P), ITQ-1(P), SSZ-25(P),            and mixtures of two or more thereof, wherein more preferably            the layered precursor comprises MCM-22(P) and/or SSZ-25(P),            preferably MCM-22(P), and wherein more preferably MCM-22(P)            is employed as the seed crystals in the mixture prepared            in (i) and crystallized in (ii).

    -   41. The process of any of embodiments 1 to 40, wherein the seed        crystals comprise a zeolitic material having an MWW framework        structure, wherein the zeolitic material is preferably selected        from the group consisting of MCM-22, [Ga—Si-0]-MWW,        [Ti—Si—O]-MWW, ERB-1, ITQ-1, PSH-3, SSZ-25, and mixtures of two        or more thereof,        -   wherein the zeolitic material is more preferably selected            from the group consisting of MCM-22, ITQ-1, SSZ-25, and            mixtures of two or more thereof,        -   wherein more preferably the zeolitic material comprises            MCM-22 and/or SSZ-25, preferably MCM-22, and wherein more            preferably MCM-22 is employed as the seed crystals in the            mixture prepared in (i) and crystallized in (ii).

    -   42. The process of any of embodiments 1 to 41, wherein after        preparing the mixture in (i) and prior to its crystallization        in (ii) the mixture is homogenized, preferably by mixing, and        more preferably by grinding and/or milling, more preferably by        milling of the mixture prepared in (i).

    -   43. The process of any of embodiments 1 to 42, wherein the seed        crystals comprise a layered precursor of a zeolitic material        having an MWW framework structure as obtained and/or obtainable        in (ii) of the process of any one of embodiments 1 to 42.

    -   44. The process of any of embodiments 1 to 43, wherein the seed        crystals comprise a zeolitic material having an MWW framework        structure as obtained and/or obtainable according to the process        of any one of embodiments 1 to 42.

    -   45. A synthetic zeolitic material having an MWW framework        structure obtainable and/or obtained according to the process of        any one of embodiments 1 to 44.

    -   46. Use of a synthetic zeolitic material having an MWW framework        structure according to embodiment 45 as a molecular sieve, as an        adsorbent, preferably for ion exchange and/or for separation of        gas or liquid mixtures, as a catalyst and/or as a catalyst        component, preferably for hydrocarbon conversion, dehydration,        epoxidation, epoxide ring opening, etherification,        esterification, ammoxidation, or diesel oxidation catalysis,        more preferably for isomerization, alkylation, or epoxidation,        and wherein more preferably the zeolitic material having an MWW        framework structure is used as a catalyst for epoxidation or        alkylation, preferably for epoxidation, and more preferably for        the epoxidation of propylene to propylene oxide.

DESCRIPTION OF THE FIGURES

FIG. 1 shows the XRD (X-Ray Diffraction) patterns of the layeredprecursor B-MWW(P) obtained from Example 1 (cf. lower diffractionpattern) as well as of the B-MWW/material obtained from Example 2 aftercalcination of the layered precursor (cf. upper diffraction pattern). Inthe figure, the diffraction angle 2 theta in ° is shown along theabscissa and the relative intensities in arbitrary units are plottedalong the ordinate.

FIG. 2 shows the ²⁹Si MAS NMR of the layered precursor B-MWW(P) obtainedfrom Example 1. In the figure, the chemical shift in ppm is plottedalong the abscissa and the relative intensity is plotted in arbitraryunits along the ordinate.

FIG. 3 shows the ¹¹B 2D 3QMAS NMR of the layered precursor B-MWW(P)obtained from Example 1. In the figure, the isotropic chemical shift inppm is plotted along the ordinate to the right of the figure whereas theordinate opposite thereto displays the single dimensional isotropicspectrum. The figure further displays the second-order quadrupolarspectrum along the top of the figure, whereas the respective chemicalshift in ppm is plotted along the abscissa opposite thereto. Therelative intensities of the respective spectra are displayed inarbitrary units.

FIG. 4 shows the ²⁹Si MAS NMR of the B-MWW/ zeolitic material obtainedfrom Example 2. In the figure, the chemical shift in ppm is plottedalong the abscissa and the relative intensity is plotted in arbitraryunits along the ordinate.

FIG. 5 shows the ¹¹B 2 D 3QMAS NMR of the B-MWW/ zeolitic materialobtained from Example 2. In the figure, the isotropic chemical shift inppm is plotted along the ordinate to the right of the figure whereas theordinate opposite thereto displays the single dimensional isotropicspectrum. The figure further displays the second-order quadrupolarspectrum along the top of the figure, whereas the respective chemicalshift in ppm is plotted along the abscissa opposite thereto. Therelative intensities of the respective spectra are displayed inarbitrary units.

FIG. 6 shows the XRD (X-Ray Diffraction) patterns of the isomorphouslysubstituted layered precursor [Al,B]-MCM-22(P) obtained from Example 3.In the figure, the diffraction angle 2 theta in ° is shown along theabscissa and the relative intensities in arbitrary units are plottedalong the ordinate.

EXAMPLES

The crystallinity and phase purity of the samples were determined byX-ray powder diffraction (XRD) with a Rigaku Ultimate VI X-raydiffractometer (40 kV, 40 mA) using CuKa (λ=1.5406 ∈) radiation from 3°to 40° with 2θ.

The argon sorption isotherm for determining the BET surface area wascarried out with Micromeritics ASAP 2010M and Tristar system.

Solid-state ²⁹Si MAS NMR spectra were recorded on Varian Infinity plus400 spectrometer. ¹¹B 2 D 3QMAS NMR experiments were recorded on aBruker Infinity Plus 500 spectrometer. The elemental compositions of thesamples were determined by inductively coupled plasma (ICP) with aPerkin-Elmer 3300DV emission spectrometer.

Reference Example 1 Preparation of the Layered Precursor Al-MWW(P) usedas Seed Crystals

10.40 g of NaAlO₂ (43 weight-% Na₂O, 53 weight-% A1 ₂O₃) and 6.0 g ofNaOH were dissolved in 1239.4 g of deionied water in a 2.5 L glassbeaker. To this solution, 259 g of Ludox AS40 (40 weight-% SiO₂) and85.60 g of hexamethyleneimine were then added. The obtained gel has amolar composition of 40.28 SiO₂:1.26 Al₂O₃:3.43 Na₂O:1606 H₂O:20.13hexamethyleneimine. Said gel was transfered into a 2.5 L autoclave, andheated up to 150° C. in 1 h under a rotating speed of 100 rpm. Thecrystallization was then carried out at 150° C. for 168 h.

After the crystallization process, the white suspension obtained wasadjusted with an HNO₃ solution to reach a pH of about 6.0. Saidsuspension was then filtered, and washed with deionized water. The solidAl-MWW(P) product was dried at 120° C. for 16 h.

Example 1 Preparation of the Layered Precursor B-MWW(P) using Al-MWW(P)as Seed Crystals

0.12 g NaOH, 0.88 g orthoboric acid (H₃B0 ₃), 1.72 g solid silica gel(SiO₂. 1.16 H₂O obtained from Qingdao Haiyang Chemical Reagent Co,Ltd.), and 0.065 g Al-MCM-22(P) seed crystals obtained from ReferenceExample 1 were mixed together . After grinding for 5 min, 0.72 gcyclohexylamine was added and the resulting mixture was ground foranother 5 min to afford a gel having the molar composition 0.0665 Na₂O:1(SiO₂. 1.16H₂O):0.328 B₂O₃:0.335 cyclohexylamine including 5 wt.-% ofseed crystals based on 100 wt.-% SiO₂. Then the powder mixture wastransferred to an autoclave and sealed. After heating for 10 days at180° C., the crystallized product was filtered, washed with deionizedwater, and dried at 100° C. for 4h for obtaining the layered precursorB-MWW(P).

FIG. 1 shows the XRD of the resulting material (cf. lower diffractogramdisplayed in the figure), from which it is apparent that said producthas the structure of a layered precursor of the MWW framework structure.

The Si:B molar ratio of the obtained product is 6.7, as measured by ICPanalysis.

FIG. 2 shows the ²⁹Si MAS NMR of the layered precursor B-MWW(P). In thespectrum, the peaks of B-MCM-22(P) at −109˜−119 ppm are assigned toSi(4Si) species, whereas the peak at about −102.8 ppm is assigned toSi(3Si,1B) and/or Si(3Si,1OH).

FIG. 3 shows the ¹¹B 2 D 3QMAS NMR of the layered precursor B-MWW(P).The 2 D 3QMAS spectrum was sheared so that the F1 axis is the isotropicchemical shift dimension and the F2 axis contains the second-orderquadrupolar line shape. The 2 D contours reveal that there exist twodistinct B sites: B[4] species stemming from tetrahedral boroncoordination in the framework, and B[3] species stemming fromextra-framework boron in trigonal coordination.

Example 2 Preparation of B-MWW from the Layered Precursor

1 g of layered precursor B-MWW(P) as obtained from Example 1 was placedin 50 ml of 1 M NH₄NO₃ solution, and the solution was heated to 80° C.for 1 h, after which solid product was isolated. The procedure wasrepeated twice. The solid product was then calcined at 550° C. for 5 hfor obtaining the B-MWW zeolitic material.

FIG. 1 shows the XRD of the resulting material (cf. upper diffractogramdisplayed in the figure), from which it is apparent that said producthas the MWW framework structure.

The BET specific surface area of the B-MWW product was determined to be391 m²/g.

FIG. 4 shows the ²⁹Si MAS NMR of the B-MWW product, wherein the peaksare all assigned to Si(4Si) species. In particular, compared to thespectrum of the layered precursor, the peak at about −102.5 ppm assignedto Si(3Si,1B) and/or Si(3Si,1OH) for the layered precursor is shifted to−105.2 ppm after calcination, indicating that the Si(3Si,1OH) speciesbetween the layers of the precursor become Si(4Si) species in the B-MWWproduct due to the condensation of hydroxyl between the layers of theprecursor material.

FIG. 5 shows the ¹¹B 2 D 3QMAS NMR of the B-MWW product. The 2 D 3QMASspectrum was again sheared so that the F1 axis is the isotropic chemicalshift dimension and the F2 axis contains the second-order quadrupolarline shape. The ‘sheared’ 2 D ¹¹B MQ-MAS spectrum of the B-MWW zeoliteobtained upon calcination clearly shows the presence of three distinctboron signals assigned to boron in tedrahedral (BTET), distortedtetrahedral (BD.TET), and octahedrally coordinated (Baur) environments,wherein the isotropic ¹¹B chemical shifts calculated for the resonancesare around −4.4 (Boc-r), 13.3 (BD.TET), and 19.0 (B_(TET)) ppm. Thisresult clearly indicates that deboronation has occurred to a certainextent upon calcination at 550° C.

Example 3 Isomorphous Substitution of the Layered Precursor of B-MWWwith Al

0.2 g of layered precursor B-MWW(P) as obtained from Example 1 placed in20 g of a 0.15 M Al(NO₃)₃ solution which was then heated to 100° C. for4 days for isomorphously substituting boron against aluminum. The solidwas then isolated for obtaining an isomorphously substituted layeredprecursor [Al,B]-MCM-22(P). The Si:Al molar ratio of the obtainedproduct is 10.3 and the Si:B molar ratio is 30.7, as respectivelymeasured by ICP analysis.

FIG. 6 shows the XRD of the resulting material, from which it isapparent that said product has the structure of a layered precursor ofthe MWW framework structure.

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1.-15. (canceled)
 16. A process for producing a zeolitic material havingan MWW framework structure comprising YO₂ and B₂O₃, wherein Y stands fora tetravalent element, the process comprising: (i) mixing one or moresources for YO₂, one or more sources for B₂O₃, one or moreorganotemplates, and seed crystals, to obtain a mixture; (ii)crystallizing the mixture to obtain a layered precursor of the MWWframework structure; and (iii) calcining the layered precursor to obtainthe zeolitic material having the MWW framework structure, wherein: theone or more organotemplates have the formula (I)R¹R²R³N   (I) R¹ is (C₅-C₈)cycloalkyl, R² and R³ are independently fromeach other H or alkyl; and the mixture and the layered precursorcomprise 35 wt.-% or less of H₂O based on 100 wt.-% of YO₂ contained inthe mixture and the layered precursor.
 17. The process of claim 16,wherein the mixture and the layered precursor comprise 5 wt.-% or lessof fluoride calculated as the element and based on 100 wt.-% of YO₂. 18.The process of claim 16, wherein the mixture and the layered precursorcomprise 5 wt.-% or less of P and/or Al calculated as the respectiveelement and based on 100 wt.-% of YO₂.
 19. The process of claim 16,wherein the layered precursor is selected from the group consisting ofB-MCM-22(P), B-ERB-1(P), B-ITQ-1(P), B-PSH-3(P), B-SSZ-25(P), andmixtures of two or more thereof.
 20. The process of claim 16, whereinthe zeolitic material having the MWW framework structure is selectedfrom the group consisting of B-MCM-22, B-ERB-1, B-ITQ-1, B-PSH-3,B-SSZ-25, and mixtures of two or more thereof.
 21. The process of claim16, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr,Ge, and combinations of two or more thereof.
 22. The process of claim16, wherein apart from organotemplate optionally contained in the seedcrystals, the mixture does not contain piperidine or hexamethyleneimine.23. The process of claim 16, wherein the crystallization is conductedunder autogenous pressure.
 24. The process of claim 16, wherein afterafter the crystallizing and prior to the calcining, the process furthercomprises (a) isolating the layered precursor , to obtain an isolatedlayered precursor; (b) optionally washing the isolated layeredprecursor, to obtain a washed layered precursor; (c) optionally dryingthe isolated layered precursor or the washed layered precursor, toobtain a dried layered precursor; (d) optionally subjecting the layeredprecursor, the isolated layered precursor, or the washed layeredprecursor, or the dried layered precursor to ion exchange, to obtain anion exchanged layered precursor; and (e) optionally subjecting theisolated layered precursor, or the washed layered precursor, or thedried layered precursor, or the ion exchanged layered precursor toisomorphous substitution.
 25. The process of claim 24, wherein theisomorphous substitution is performed such that boron in the frameworkstructure of the isolated layered precursor, the dried layeredprecursor, or the ion exchanged layered precursor is isomorphouslysubstituted against one or more trivalent and/or tetravalent elements.26. The process of claim 16, wherein the calcination is carried out at atemperature of from 300 to 900° C.
 27. The process of claim 16, furthercomprising, after the calcining: (iv) deboronating the zeolitic materialhaving the MWW framework structure with a liquid solvent system, therebyobtaining a deboronated zeolitic material having an MWW frameworkstructure.
 28. The process of claim 27, wherein the deboronation iscarried out at a temperature of from 50 to 125° C.
 29. A syntheticzeolitic material having an MWW framework structure obtained by theprocess of claim
 16. 30. A composition comprising the synthetic zeoliticmaterial of claim 29, wherein the composition is selected from the groupconsisting of a molecular sieve, an adsorbent, a catalyst a catalystcomponent, and combinations thereof.